Bioaccumulation of persistent organic pollutants in lichen-caribou-wolf food chains of Canada's Central and Western Arctic

While biomagnification of persistent organic pollutants (POPs) in aquatic food chains is well documented, there have been few investigations of the trophodynamics of POPs in Arctic terrestrial food chains. This study presents field-collected concentration data and corresponding fugacities of various hydrophobic organic chemicals (ranging in octanol-water partition coefficients or K(OW) from approximately 10(3.8) to 10(9)) in two lichen species (Cladina rangiferina and Cetraria nivalis), willow leaves (Salix glauca), barren-ground caribou (Rangifer tarandus), and wolves (Canis lupus) from Canada's Central and Western Arctic region. The results show that, in contrast to aquatic food chains, persistent substances including beta-hexachlorocyclohexane and 1,2,4,5-tetrachlorobenzene with a K(OW) <10(5) can substantially biomagnify in lichen-caribou-wolf food chains in Canada's Central and Western Arctic. Strong positive correlations between the biomagnification factor and the octanol-air partition coefficients (K(OA)) of nonmetabolizable compounds were observed in wolves. In caribou, the biomagnification factors dropped slightly with increasing K(OA). K(OA) proved to be a better indicator of biomagnification than K(OW). Current management policies that consider only chemicals with K(OW) values >10(5) as bioaccumulative substances fail to identify substances that have the potential to biomagnify in Arctic terrestrial food chains despite a low K(OW) because of a high K(OA).     

Trophic magnification of PCBs and Its relationship to the octanol-water partition coefficient

We investigated polychlorinated biphenyl (PCB) bioaccumulation relative to octanol-water partition coefficient (K(OW)) and organism trophic position (TP) at the Lake Hartwell Superfund site (South Carolina). We measured PCBs (127 congeners) and stable isotopes (δ1?N) in sediment, organic matter, phytoplankton, zooplankton, macroinvertebrates, and fish. TP, as calculated from δ1?N, was significantly, positively related to PCB concentrations, and food web trophic magnification factors (TMFs) ranged from 1.5-6.6 among congeners. TMFs of individual congeners increased strongly with log K(OW), as did the predictive power (r2) of individual TP-PCB regression models used to calculate TMFs. We developed log K(OW)-TMF models for eight food webs with vastly different environments (freshwater, marine, arctic, temperate) and species composition (cold- vs warmblooded consumers). The effect of K(OW) on congener TMFs varied strongly across food webs (model slopes 0.0-15.0) because the range of TMFs among studies was also highly variable. We standardized TMFs within studies to mean = 0, standard deviation (SD) = 1 to normalize for scale differences and found a remarkably consistent K(OW) effect on TMFs (no difference in model slopes among food webs). Our findings underscore the importance of hydrophobicity (as characterized by K(OW)) in regulating bioaccumulation of recalcitrant compounds in aquatic systems, and demonstrate that relationships between chemical K(OW) and bioaccumulation from field studies are more generalized than previously recognized.     

A terrestrial food-chain bioaccumulation model for POPs

Mechanistic bioaccumulation models for fish and piscivorous food-webs are widely used to assess the environmental hazard and risk of commercial chemicals, develop water quality criteria and remediation objectives, and conduct exposure assessment of pesticides in aquatic systems. Similar models for mammals and terrestrial food-webs are largely absent. As a result, the hazards and risks of bioaccumulative substances in mammals, birds, and humans remain unrecognized by regulators, and current globally used criteria for identifying bioaccumulative substances only apply to water-breathing organisms and are inadequate for protecting air-breathing organisms including mammals, birds, and human beings. In this paper, we develop and test a modeling framework that can be used to estimate the biomagnification potential and the organism-soil bioaccumulation factor of organic commercial chemicals in terrestrial food-chains. We test the model for the soil-earthworm-shrew food-chain and apply the model to illustrate that (i) chemicals with an octanol-air partition coefficient (K(OA)) < 10(5.25) do not biomagnify even if the K(ow) is high and optimal for biomagnification in fish; (ii) chemicals with a K(OA) > or = 105.25 and a K(ow) between 10(1.75) and 10(12) have a biomagnification potential unless they are metabolized at a sufficiently rapid rate (e.g., in excess of 0.3 d(-1) or a half-life time of 2.5 d for shrews).     

Assessing model uncertainty of bioaccumulation models by combining chemical space visualization with a process-based diagnostic approach

As models describing human exposure to organic chemicals gain wider use in chemical risk assessment and management, it becomes important to understand their uncertainty. Although evaluation of parameter sensitivity/uncertainty is increasingly common, model uncertainty is rarely assessed. When it is, the assessment is generally limited to a handful of chemicals. In this study, a strategy for more comprehensive model uncertainty assessment was developed. A regulatory model (EUSES) was compared with a research model based on more recent science. Predicted human intake was used as the model end point. Chemical space visualization techniques showed that the extent of disagreement between the models varied strongly with chemical partitioning properties. For each region of disagreement, the primary human exposure vector was determined. The differences between the models' process algorithms describing these exposure vectors were identified and evaluated. The equilibrium assumption for root crops in EUSES caused overestimations in daily intake of superhydrophobic chemicals (log K(OW) > 11, log K(OA) > 10), whereas EUSES's approach to calculating bioaccumulation in fish prey resulted in underestimations for hydrophobic compounds (log K(OW) ～ 6-8). Uptake of hydrophilic chemicals from soil and bioaccumulation of superhydrophobic chemicals in zooplankton were identified as important research areas to enable further reduction of model uncertainty in bioaccumulation models.     

Bioamplification and the selective depletion of persistent organic pollutants in Chinook salmon larvae

The maternal provisioning of yolk to eggs transfers significant quantities of persistent organic pollutants (POPs). As yolk utilization progresses via metabolic activity, there is a potential to realize further increases in POP concentrations if yolk lipids are depleted at a faster rate than POPs, a condition referred to as bioamplification. This study investigated the bioamplification of POPs in Chinook salmon ( Oncorhynchus tshawytscha ) eggs and larvae. Chinook eggs were sampled from the Credit River, ON, Canada, and brought to an aquaculture facility where they were fertilized, incubated, and maintained posthatch until maternally derived lipid reserves became depleted (approximately 168 days). The loss of chemicals having an octanol-water partition coefficient (log K(OW)) greater than 5.8 was slow to negligible from days 0-135. However, during the increase in water temperatures in early spring, K(OW)-dependent elimination of POPs was observed. Bioamplification was maximized for the highest log K(OW) POPs, with an approximate 5-fold increase in lipid equivalents concentrations in 168 day old larvae as compared to newly fertilized eggs. This study demonstrates that later yolk-sac Chinook larvae (before exogenous feeding) are exposed to higher lipid equivalents POP concentrations than predicted by maternal deposition, which could lead to underestimates in the toxicity of critical life stages.     

Biological pump control of the fate and distribution of hydrophobic organic pollutants in water and plankton

The goal of this study was to experimentally assess the coupling between primary producer biomass dynamics and the distribution and fate of persistent organic pollutants (POPs) in a lake pelagic ecosystem. This was done by following the short-term evolution of polychlorinated biphenyl (PCB) concentrations in water and biota (phytoplankton and zooplankton) and the variability of bioconcentration (BCF), biomagnification (BMF), and bioaccumulation (BAF) factors during the development of a typical spring ecological progression in which the phytoplankton bloom is followed by a peak in the zooplankton abundance. The bulk of compounds with log K(OW) > 6.5 in the lake epilimnion was mainly associated with primary producer biomass. The phytoplankton biological pump was a major driver of POP export from the epilimnion, causing the decline of dissolved-phase concentrations. The BCF of phytoplankton for the more hydrophobic PCBs showed minima during the period of biomass climax. The concentration in the zooplankton of all selected PCBs sharply declined from March to May, with BAFs having minima in the post algal bloom phase. Biomagnification occurred during the pre algal bloom and algal bloom phases but appeared to be absent during the post algal bloom. This study highlights the occurrence of a prompt and complex response in the fate and distribution of POPs to dynamic biogeochemical control. Within the frame of the ecological succession, phytoplankton and zooplankton biomass dynamics produced bioaccumulation metrics varying over 1-2 orders of magnitude in the time frame of a few weeks and resulted in reduced trophic web exposure.     

Combining long-range transport and bioaccumulation considerations to identify potential Arctic contaminants

The identification of potential Arctic contaminants requires an assessment of both the long-range transport and the bioaccumulation of the chemicals, most particularly in the indigenous inhabitants of the Arctic. For this purpose, a nonsteady state, zonally averaged global distribution model was linked to a nonsteady state bioaccumulation model describing Inuit exposure from a marine diet. The potential of hypothetical, perfectly persistent chemicals with varying combinations of partitioning properties to enrich in the Arctic environment following emission in the lower latitudes and, additionally, to bioaccumulate in the Arctic food chains was evaluated using the Arctic contamination and bioaccumulation potential (AC-BAP). The AC-BAP is defined as the quotient of the human body burden of the chemical and the quantity of chemical cumulatively emitted to the global environment. The highest AC-BAP values (up to 3.7 x 10(-11) person(-1)) were obtained for hypothetical multimedia chemicals with intermediate volatility and hydrophobicity. Perfectly persistent chemicals with 3.5 < log K(OW) < 8.5 and log K(OA) > 6 had AC-BAP values of at least 10% of the maximum value, indicating that a broad range of chemicals are potential Arctic contaminants if they are persistent. Moreover, the simulation results suggest that a chemical's potential to bioaccumulate has a stronger impact on the overall potential to become an Arctic contaminant in humans than its potential for long-range transport. This modeling exercise demonstrates how linking nonsteady state models of chemical bioaccumulation and of global chemical fate can provide a valuable tool for assessing a chemical's potential to be a contaminant in remote regions.     

How do the partitioning properties of polyhalogenated POPs change when chlorine is replaced with bromine?

Information about the mobility and the partitioning properties of brominated persistent organic pollutants, the environmental levels of which are sometimes higher than those of the chlorinated analogues, is limited. We estimated n-octanol/ water (log K(OW)), n-octanol/air (log K(OA)), and air/water (log K(AW)) partition coefficients for 1436 chloro- and bromo-analogues of dibenzo-p-dioxins, dibenzofurans, biphenyls, naphthalenes, diphenyl ethers, and benzenes by employing quantitative structure-property relationship (QSPR) techniques. The searches for similar partitioning patterns were performed by means of two-dimensional cluster analysis. Five classes of compounds were identified. Each of the class is characterized by similar partition coefficients and, in consequence, similar environmental properties. Finally the data was fitted into a simple multimedia model involving the partitioning map. In addition, we found thatthe changes in the partition coefficients upon the replacement of chlorine with bromine were constant: 0.11, 0.31, and -0.21 per bromine atom for log K(OW), log K(OA), and log K(AW), respectively. On the basis of this observation, a method for rapid estimation of changes in the partition coefficient upon chlorine-bromine substitution was proposed.     

Modeling decreased food chain accumulation of PAHs due to strong sorption to carbonaceous materials and metabolic transformation

The predictive power of bioaccumulation models may be limited when they do not accountfor strong sorption of organic contaminants to carbonaceous materials (CM) such as black carbon, and when they do not include metabolic transformation. We tested a food web accumulation model, including sorption to CM, on data from a model ecosystem experiment with historically contaminated sediment. In combination with measured CM contents of the sediment, the model gave good fits for the biota that are known not to metabolize PAHs (macrophytes, periphyton, floating algal biomass). The same model was applied to invertebrates and fish but now with optimization of their metabolic transformation rates (k(m)). For fish, these rates correlated empirically with log K(OW): Log k(m) = -0.8 log K(OW) + 4.5 (r2 adj = 0.73). For invertebrates, log k(m) did not correlate with logK(OW). Sensitivity analysis revealed that the model output is highly sensitive to sediment CM content and sorption parameters, moderately sensitive to metabolic transformation rates, and slightly sensitive to lipid fraction of the organism and diet-related parameters. It is concluded that CM-inclusive models yield a better assessment of accumulation than models without sorption to CM. Furthermore, inclusion of CM in a model enables metabolic transformation rates to be calculated from the remaining overestimation in the model results when compared to measured data.     

The influence of vertical sorbed phase transport on the fate of organic chemicals in surface soils

Gaseous exchange between surface soil and the atmosphere is an important process in the environmental fate of many chemicals. It was hypothesized that this process is influenced by vertical transport of chemicals sorbed to soil particles. Vertical sorbed phase transport in surface soils occurs by many processes such as bioturbation, cryoturbation, and erosion into cracks formed by soil drying. The solution of the advection/diffusion equation proposed by Jury et al. to describe organic chemical fate in a uniformly contaminated surface soil was modified to include vertical sorbed phase transport This process was modeled using a sorbed phase diffusion coefficient, the value of which was derived from soil carbon mass balances in the literature. The effective diffusivity of the chemical in a typical soil was greater in the modified model than in the model without sorbed phase transport for compounds with log K(OW) > 2 and log K(OA) > 6. Within this chemical partitioning space, the rate of volatilization from the surface soil was larger in the modified model than in the original model by up to a factor of 65. The volatilization rate was insensitive to the value of the sorbed phase diffusion coefficient throughout much of this chemical partitioning space, indicating that the surface soil layer was essentially well-mixed and that the mass transfer coefficient was determined by diffusion through the atmospheric boundary layer only. When this process was included in a non-steady-state regional multimedia chemical fate model running with a generic emissions scenario to air, the predicted soil concentrations increased by upto a factor of 25,whilethe air concentrations decreased by as much as a factor of approximately 3. Vertical sorbed phase transport in the soil thus has a major impact on predicted air and soil concentrations, the state of equilibrium, and the direction and magnitude of the chemical flux between air and soil. It is a key process influencing the environmental fate of persistent organic pollutants (POPs).     

Bioavailability of PAHs in aluminum smelter affected sediments: evaluation through assessment of pore water concentrations and in vivo bioaccumulation

Bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) from coal tar pitch polluted sediments was predicted by (1) a generic approach based on organic carbon-water partitioning and Gibbs linear free energy relationship (between K(OW) and K(OC)), and (2) measurements of freely dissolved concentrations of PAHs in the sediment pore water, using passive samplers and solid phase extraction. Results from these predictions were compared with those from in vivo bioaccumulation experiments using Nereis diversicolor (Polychaeta), Hinia reticulata (Gastropoda), and Nuculoma tenuis (Bivalvia). Measured sediment/water partition coefficients were higher than predicted by the generic approach. Furthermore, predicted biota-to-sediment accumulation factors (BSAFs) derived from measured pore water concentrations were more in agreement with the bioaccumulation observed for two of the three species. Discrepancies associated with the third species (N. tenuis) were likely a result of particles remaining in the intestine (as shown by microscopic evaluation). These results indicate the importance of conducting site-specific evaluations of pore water concentrations and/or bioaccumulation studies by direct measurements to accurately provide a basis for risk assessment and remediation plans. The importance of knowledge regarding specific characteristics of model organisms is emphasized.     

Polyethylene devices: passive samplers for measuring dissolved hydrophobic organic compounds in aquatic environments

We demonstrate the use of polyethylene devices (PEDs) for assessing hydrophobic organic compounds (HOCs) in aquatic environments. Like semipermeable membrane devices (SPMDs) and solid-phase microextraction (SPME), PEDs passively accumulate HOCs in proportion to their freely dissolved concentrations. Polyethylene-water partition constants (K(PEW)S) were measured in the laboratory for eight polycyclic aromatic hydrocarbons (PAHs), five polychlorinated biphenyls (PCBs), and one polychlorinated dibenzop-dioxin (PCDD), and these were found to correlate with octanol-water partition constants (K(OW)s; log K(PEW) = 1.13 log K(OW) - 0.86, R2 = 0.89). Temperature and salinity dependencies of K(PEW) values for the HOCs tested were well predicted with excess enthalpies of solution in water and Setschenow constants, respectively. We also showed that standards, impregnated in the PED before deployment, can be used to correct for incomplete equilibrations. Using PEDs, we measured phenanthrene and pyrene at ng/L concentrations and 2,2',5,5'-tetrachlorobiphenyl at pg/L concentrations in Boston Harbor seawater, consistent with our findings using traditional procedures. PEDs are cheap and robust samplers, competent to accomplish in situ, time-averaged passive sampling with fast equilibration times (approximately days) and simplified laboratory analyses.     

Biogeochemical cycling of methylmercury in lakes and tundra watersheds of Arctic Alaska

The fate of atmospherically deposited and environmentally active Hg is uncertain in the Arctic, and of greatest toxicological concern is the transformation to monometh-ylmercury (MMHg). Lake/watershed mass balances were developed to examine MMHg cycling in four northern Alaska lakes near the ecological research station at Toolik Lake (68 degrees 38' N, 149 degrees 36' W). Primary features of the cycle are watershed runoff, sedimentary production and mobilization, burial, and photodecomposition in the water column. The principal source of MMHg is in situ benthic production with 80-91% of total inputs provided by diffusion from sediments. The production and contribution of MMHg from tundra watersheds is modest. Photodecomposition, though confined to a short ice-free season, provides the primary control for MMHg (66-88% of total inputs) and greatly attenuates bioaccumulation. Solid-phase MMHg and gross potential rates of Hg methylation, assayed with an isotopic tracer, vary positively with the level of inorganic Hg in filtered pore water, indicating that MMHg production is Hg-limited in these lakes. Moreover, sediment-waterfluxes of MMHg (i.e., net production at steady state) are related to sediment Hg loadings from the atmosphere. These results suggest that loadings of Hg derived from atmospheric deposition are a major factor affecting MMHg cycling in arctic ecosystems. However, environmental changes associated with warming of the Arctic (e.g., increased weathering, temperature, productivity, and organic loadings) may enhance MMHg bioaccumulation by stimulating Hg methylation and inhibiting photodecomposition.     

Partitioning and bioaccumulation of PBDEs and PCBs in Lake Michigan

Water from Lake Michigan and fish from all five Great Lakes have been sampled and analyzed for a suite of six polybrominated diphenyl ether (PBDE) congeners and 110 polychlorinated biphenyl congeners (PCBs). The Lake Michigan dissolved phase PBDE congener concentrations (0.2 to 10 pg/L) are similar to dissolved phase PCB congener concentrations (nondetected to 13 pg/L). Partitioning of PBDEs between the particulate and dissolved phases exhibits behavior similar to that of PCBs. Organic-carbon-normalized water-particle partition coefficients (log K(OC)s) ranged from 6.2 to 6.5. Lake trout are depleted in BDE-99 relative to dissolved phase concentrations, and in contrast to what is expected from the PCB congener patterns. This reflects suspected debromination of BDE-99 in the food web of Lake Michigan. A regression of the log of the bioaccumulation factor (BAF) and the log of the octanol-water partition coefficent (K(OW)) indicated a positive relationship for both PCB congeners and PBDE congeners. BDE-99 does not appear to followthe same trend, a further indication that it is subject to biotransformation. Using the PBDE BAFs for Lake Michigan and the PBDE fish concentrations from the other Great Lakes it is expected that the dissolved phase concentrations of congeners in the other lakes would range from 0.04 to approximately 3 pg/L.     

Indoor and outdoor air concentrations and phase partitioning of perfluoroalkyl sulfonamides and polybrominated diphenyl ethers

Perfluoroalkyls (PFAs) and polybrominated diphenyl ethers (PBDEs) are two classes of emerging persistent organic pollutants (POPs) that are widely used in domestic and workplace products. These compounds also occur in remote locations such as the Arctic where they are accumulated in the food chain. This study makes connections between indoor sources of these chemicals and the potential and mode for their transport in air. In the case of the PFAs, three perfluoralkyl sulfonamides (PFASs) were investigated--N-methyl perfluorooctane sulfonamidoethanol (MeFOSE), N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE), and N-methyl perfluorooctane sulfonamidethylacrylate (MeFOSEA). These are believed to act as precursors that eventually degrade to perfluorooctane sulfonate (PFOS), which is detected in samples from remote regions. High-volume samples were collected for indoor and outdoor air to investigate the source signature and strength. Mean indoor air concentrations (pg/m3) were 2590 (MeFOSE), 770 (EtFOSE), and 630 (sigmaPBDE). The ratios of concentration between indoor and outdoor air were 110 for MeFOSE, 85 for EtFOSE, and 15 for sigmaPBDE. The gas and particle phases were collected separately to investigate the partitioning characteristics of these chemicals. Measured particulate percentages were compared to predicted values determined using models based on the octanol-air partition coefficient (K(OA)) and supercooled liquid vapor pressure (pL(o)); these models were previously developed for nonpolar, hydrophobic chemicals. To make this comparison for the three PFASs, it was necessary to measure their K(OA) and vapor pressure. K(OA) values were measured as a function of temperature (0 to +20 degrees C). Values of log K(OA) at 20 degrees C were 7.70, 7.78, and 7.87 for MeFOSE, EtFOSE, and MeFOSEA, respectively. Partitioning to octanol increased at colder temperatures, and the enthalpies associated with octanol-air transfer (deltaH(OA), kJ/mol) were 68-73 and consistent with previous measurements for nonpolar hydrophobic chemicals. Solid-phase vapor pressures (pS(o)) were measured at room temperature (23 degrees C) by the gas saturation method. Values of pS(o) (Pa) were 4.0 x 10(-4), 1.7 x 10(-3), and 4.1 x 10(-4), respectively. These were converted to pL(o) for describing particle-gas exchange. Both the pL(o)-based model and the K(OA) model worked well for the PBDEs but were not valid for the PFASs, greatly underpredicting particulate percentages. These results suggest that existing K(OA)- and pL(o)-based models of partitioning will need to be recalibrated for PFASs.     

Photodecomposition of methylmercury in an Arctic Alaskan lake

Sunlight-induced decomposition of monomethylmercury (MMHg) reduces its availability for accumulation in aquatic food webs. We examined MMHg degradation in epilimnetic waters of Toolik Lake (68 degrees 38' N, 149 degrees 36' W) in arctic Alaska, a region illuminated by sunlight almost continuously during the summer. MMHg decomposition in surface water of Toolik Lake is exclusively abiotic and mediated by sunlight; comparable rates of MMHg decomposition were observed in filter-sterilized and unfiltered surface waters incubated under in situ sunlight and temperature conditions, and no MMHg was degraded in unfiltered aliquots incubated in the dark. Rates of photodecomposition are first order with respect to both MMHg concentration and the intensity of photosynthetically active radiation (PAR), except at the lake surface where rates of photochemical degradation are enhanced relative to PAR intensity and may be attributed to an additional influence of ultraviolet light. The estimated annual loss of MMHg to photodecomposition in Toolik Lake, though limited to a 100-d ice-free season, accounts for about 80% of the MMHg mobilized annually from in situ sedimentary production, the primary source in Toolik Lake. These results suggest that greater light attenuation in lacustrine surface waters, a potential result of increased loadings of dissolved organic matter due to continued warming in the Arctic, may result in less photodecomposition and subsequently greater availability of MMHg for bioaccumulation.     

Estimating phospholipid membrane-water partition coefficients using comprehensive two-dimensional gas chromatography

Recent studies have shown that membrane-water partition coefficients of organic chemicals can be used to predict bioaccumulation and type I narcosis toxicity more accurately than the traditional K(OW)-based approach. In this paper, we demonstrate how comprehensive two-dimensional gas chromatography (GC × GC) can be used to estimate such membrane-water partition coefficients (K(PLW)s), focusing in particular on phosphatidyl choline based lipids. This method performed well for a set of 38 compounds, including polycyclic aromatic hydrocarbons, polychlorinated benzenes and biphenyls, and substituted benzenes including some phenols and anilines. The average difference between the estimated and the measured log K(PLW) values of 0.47 log units is smaller than in the case of a log K(OW) correlation approach but larger than seen using a polyparameter linear free energy relationship based approach. However, the GC × GC based method presents the advantage that it can be applied to mixtures of chemicals that are not completely identified, such as petroleum hydrocarbon mixtures. At the same time, our application of the GC × GC method suffered larger errors when applied to certain hydrogen bonding compounds due to the inability of the GC × GC capillary columns phases that we used to interact with analytes via hydrogen bond donation/electron acceptance.     

Accumulation and depuration of polychlorinated biphenyls from field-collected sediment in three freshwater organisms

As laboratory-based bioaccumulation methods are standardized and expanded to include other test species, kinetic studies assessing the major classes of contaminants with these species are needed to adequately select the standard duration for bioaccumulation tests. In the present study we measured the uptake (28-d exposure) of polychlorinated biphenyls (PCBs; total and selected congeners) from field-contaminated sediment in the oligochaete Lumbriculus variegatus, mayfly nymph Hexagenia spp., and fathead minnow Pimephales promelas. Depuration (25 d) of PCBs was measured in organisms that had been transferred to clean sediment after the 28-d exposure. Uptake and elimination of PCBs was rapid in L. variegatus and Hexagenia spp. Tissue residues reached steady-state concentrations within 28 d; elimination rates and biota-sediment accumulation factors (BSAFs) of the PCB congeners were not correlated with K(OW). Uptake and elimination rates of PCBs were slower in P. promelas, and it is not clear whether steady-state was reached in fish tissues. Elimination rates of the PCB congeners significantly decreased with increasing K(OW) in fish. The appropriateness of a 28-d exposure for measuring steady-state concentrations in tissue of the invertebrates was confirmed, but further study is required for fish.     

Sorption of polycyclic aromatic hydrocarbons to oil contaminated sediment: unresolved complex?

Oil is ubiquitous in aquatic sediments and may affect partitioning and bioavailability of hydrophobic organic chemicals (HOCs). In contrast to other sedimentary hydrophobic carbon phases (natural organic matter, soot-like materials), oil residues have hardly received any attention as far as it concerns effects on HOC sorption. This paper describes experimental work dealing with such effects of oil on polycyclic aromatic hydrocarbon (PAH) sorption to sediments. Three different oils were spiked to a marine sediment in concentrations between 0 and 100 g/kg. Sediment-water distribution coefficients (Kd) for six deuterated PAHs were then determined either directly after spiking the oil or after a semi-natural weathering process in the lab (lasting for more than 2 yr). Resulting Kd values demonstrated sorption-reducing (competitive) effects at relatively low oil concentrations and sorption-enhancing effects at high oil concentrations. The latter effects only occurred above a certain threshold [i.e., ca. 15% (w/w) of oil on a sedimentary organic carbon basis] marking the oil concentration at which the hydrocarbon mixture presumably starts forming separate phases. Assuming a two-domain (organic carbon + oil) distribution model, oil-water distribution coefficients (K(oil)) for PAHs were estimated. For fresh oils, log K(oil) values appeared to be very similar for different types of oils, proportional to log K(OW) values and indistinguishable from log K(OC) values. For weathered oils, K(oil) values were also rather independent of the type of oil, but the affinity of low molecular weight PAHs for weathered oil residues appeared to be extremely high, even higher than values reported for most types of soot. Because affinities of high molecular weight PAHs for oils had not changed upon weathering, sorption of all PAHs studied (comprising a log K(OW) range of 4.6-6.9) to the weathered oil residues appeared to be more or less constant (averaged log K(oil) = 7.0 +/- 0.24). These results demonstrate that it is crucial to take the presence of oil and its weathering state into account when assessing the actual fate of PAHs in aquatic environments.     

Measured pore-water concentrations make equilibrium partitioning work--a data analysis

There is an increasing body of evidence that the bioaccumulation of sediment-associated hydrophobic organic compounds (HOCs) is strongly influenced by sequestration. At present, it is not known how equilibrium partitioning theory (EqP), the most commonly employed approach for describing sediment bioaccumulation can be applied to sediments with sequestered contaminants. In this paper, we present freely dissolved pore-water concentrations of HOCs. These data were employed to interpret sediment bioaccumulation and sequestration data in order to arrive at a process based evaluation of EqP. The data analysis suggests that sediment bioaccumulation of compounds up to log K(ow) 7.5 in Tubificidae can be described as bioconcentration from pore-water. In addition, the pore-water concentrations of HOCs (4.5 < log K(ow) < 7.5) are established by equilibrium partitioning between the rapidly desorbing HOCs fraction in the sediment and the pore-water. Taken together, these findings indicate that EqP is a conceptually correct representation of sediment bioaccumulation, provided that sequestration is accounted for. This implies that the risk assessment of sediment-associated HOCs can be significantly simplified: With a method at hand for measuring freely dissolved pore-water concentrations of HOCs, it appears that HOCs' body residues in sediment dwelling organisms can be estimated on the basis of concentrations in pore-water and bioconcentration factors.